Apparatus for manufacturing hydrogen peroxid.



M Patented Oct. 3,1899. 8. BUSENBLUM &. 6. J. YABNBLD. APPARATUS FOR IANUFAGTURINB HYDROGEN PEBDXID.

(Applicnflan filed D06. 31, 1897. {No Model.) a Sheets-Sheet 1 Wznussgsp Janna-toms;

No. 634,093. Patented Oct. 3,1899. 8. ROSENBLUM & C. J. YARNULD.

' APPARATUS FOR MANUFACTURING HYDBUGEN PEBOXID.

(Application flied Dec.,31, 1897. (No Model.) 3 Shams-Sheet 2 J7 J J 'JJ JF- J A J A J wtnessqs ja /anions:

mam/ 4 m.-sa4,o9a.. Patented Oct. 3, I899.

" s. BOSENBLUM & c. .2. YABNOLD. r APPARATUS FOR HANUFAGTURING HYDROGEN PEROXID.

(Applicstian filed Doc. 31, 1897.)

(In Model.) 3 She!s$heet 3.

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UNITED STATES PATENT OFFIC SIGMUND ROSENBLUM AND CHARLES JonN xAnNoL'D, on Lonoo ENG- LAND, ASSIGNORS 'ro- THE ooMM RoIAL ozone SYNDICATE, LIMITED, oFsAME PLACE.

APPARATUS FOR MANUFACTURING HYDROGEN PEROXID.

SPECIFICATION forming; part of Letters Patent No. 634,093, dated October 8, 18 99. Applicction filed December 31, 1897. Serial No. 664,954. (No model.)

To all whom it may concern: However, the yield of hydrogen peroxide Be itknown that we, SIGMUND ROSENBLUM, in all the above-stated reactions, it carried a subject of the Emperor of Russia, residing out in the ordinary way, is an extremely at London, and CHARLES JOHN YARNOLD, a small one and would be of no value for insubject of the Queen of England, residing atdustrial or medical purposes; but we have Brixton,London,in the county of Surrey, Engfound that by employing a method in conland, have invented certain new and useful junction with suitable apparatus hereinafter Improvements in Apparatus for the Manuto be described the yield of hydrogen peroxfacture of Hydrogen Peroxid, of which the folide in any of. the above-stated reactions can {0 lowing is a specification. be enormously increased, and thus the utili- 6o Hydrogen peroxide is at present manufaczation of these reactions for the production tured by acting on the peroxide of an alkaline of hydrogen peroxide on a largescale be made earth, preferablybarium peroxide, byan acid; possible and practicable.

The cost of this process is very considerable Of all the above-stated organic compounds 15 and has militated against a wide industrial which will yield hydrogen peroxide when actapplication of the product, and as the latter ed upon by ozone in the presence of water we when prepared by above process is very liahave selected, on account of their comparable to contain numerousimpurities it has tively'l'ow cost, the terpene and polyterpene beenhitherto impossible to apply it for med-- series of the hydrocarbons as the most suit- 20 ical and many sanitary uses. able ones for our purpose, and for the same It is well known that ozone when acting in reason we prefer to use oil or spirits of turthe presence of water upon certain organic pentine whenever a large yield of hydrogen chemical coin pounds will produce traces of peroxide at a low cost is desired.

. hydrogen peroxide. Of such compounds the Any of the above-enu merated organic com- 2 terpene series of the hydrocarbons have been pounds we may use for our purpose either found to yield to above reaction more easily single or in suitable mixtures of various prothan others. \Ve have found, however, that portions or dissolved in suitable solvents. besides these there is a whole series of or- There are numerous methods by which we ganic compounds, especially the so-called can manufacture hydrogen peroxide by the 30 unsaturated ones, among which may be action of ozone and water or ozone and steam 8o classed many of the aldehydes and ketones, upon the above-mentioned "organic 00111- the camphors, the carbohydrates of the forpounds. For instance, hydrogen peroxide mula (C H Qx, (otherwise called terpenes may be prepared by leading ozone and vapoand polyterpenes,) nearly all theetherial or rized turpentine into water, or in the place of essential oils, which mainly consist of terturpentineoneormoreof the above-n1entioned penes and polytenpenes, and alsoalarge num .organic'compounds in a vaporized condition ber of resins and balsams will when acted may be substituted, or as an alternative hyupon by ozone in the presence of wateryield drogen peroxide may be formed by leading hydrogen peroxide in a smaller or lesser de-' steam and ozone into turpentine or one or 0 gree. more of the organiccompounds mentioned The chemical change which takes place in above, which, if necessary,can be in suitable the above-stated order of reactions is not yetv solutions. The method, however, We prefer clearly known; but we presume that in the to adopt in the manufacture of hydrogen per- 7 case of the above-enumerated unsaturated or-' oxide on a commercial scale consistsinatomiz- 45 ganic compounds an-addition of ozone takes ing an emulsion or mixture of the original liq- 5 place, and peroxidesof these compounds are uid or'suitably-dissolved organic compound formed. These peroxides when acted upon or compounds with water by means of ozone, by water are decomposed into hydrogen peror, if preferred, steam maybe substituted for oxide and into the original unsaturated or water, as will be more fully described herein- 50 only'partially-oxidized compounds. after, and in carrying this principle into efwe feet we prefer to employ the apparatus shown in the accompanying drawings, of which Figure 1 is a central vertical section. Fig. 2 is an' enlarged view of a portion of Fig. 1, and Fig. 3 is a plan of Fig. 2.

Ais a cylindrical casing carried by supports A. Below it is a cylindrical vessel B, having a hermetic cover B. \Vithin the vessel is a duplex stirrer O, constituted by two sets 0 C of stirring arms or framesythe set C being carried upon a tubular shaft C and the set C carried upon a shaft 0 received concentrically within the shaft 0 Two sets of stirring frames are rotated by means of bevel or other gearing in opposite directions. In the present example the shaft 0 carries at its upper end a bevel-wheel C and the shaft C is provided with a bevel-wheel C. These twobevel-wheels are geared together by an intermediate wheel 0 which rotates the wheels 0 C and the shafts connected thereto in opposite directions, being itself driven by means of a shaft (i supported in bearings O on the top of the cover B. The lower ends of the shafts 0 G run in or upon the footstep'bearing O B is a pipe for the admission of the turpentine orothersuitable organic liquid mixed or not with water into the vessel B, and B is a drain-cock placed at the bottom of the vessel to enable the latter to be drained when desired.

B is a pipe situated at the lower part of the vessel B, which may be curved to form a coil and is perforated to allow of the passage of the ozone in small jets through the liquid above it, as shown.

In the casing A and beneath the top cover A is provided a hollow conical mounting A supporting a circular dish D, having a vertical annular flange D. In the dish D is another dish D somewhat shallower than the former.

D is a space below the dish D communieating, on the one hand, with perforations D made through the latter near its circumference, and tubular spindles D hereinafter again referred to, and, on the other hand, with the upper portion of the interior of the vessel B by way of a pipe E, controlled by a valve E. v

A pipe F, in which is a valve F, extends upward from a point near the bottom of the interior of the Vessel B through the cover B, the hollow conical mounting A and the bottom of the dish D to afford communication between the vessel B and the space D in the dish D which is closed by a cover-D perforated with tapered conical holes D having theirsmallerends uppermost. Tubularspindles D are screwed into the bottom of the dish D and have coned upper ends, which extend into the holes D There is a passage-way through the holes D around the tapered upper ends of the tubular spindles D which latter constitutes passages for the ozone, as hereinafter described, from the space D to points just below the level of the top of the cover D They can be screwed up or down to regulate the area of the an nular passage around them.

G is a pipe controlled by a valve G, affording communication between the chamber A and the interior of the vessel B.

H is a drain-pipe for draining the chamber A.

The operation is as follows: The turpentine or other suitable organic compound or mixture or suitable solution of such compounds is delivered into the vessel B through the pipe 13 in conjunction with a suitable proportion of water to form an emulsion, or the water may be introduced into the vessel separately. An emulsion is formed by rotating the stirring frames or arms 0 C in opposite directions,

and ozone, which should preferably be free from carbonic-acid gas, is then delivered into the vessel B through the perforated pipe B under any suitable pressuresay seven pounds to the square inch. The ozone passes in an upward direction through the emulsion, thereby ozonizing it, and collects at the top ofthe vessel B, thereby producing surface pressure, which forces the emulsion of turpentine and water up the pipe 1* into the space D, while some of the ozone controlled by a cock E passes up the pipe E into the space D A portion of the ozone escapes from the space D through the perforations D into the interior of the chamber A, while the remainder passes through the spindles D and draws the emulsion of turpentine and water from the space D through the tapering annular spaces of the passages D The emulsion meeting the ozone at the nozzles of the spindles D is atomized and in the form of a very fine spray is delivered, with the gas, into the interior of the chamber A, where it is met by the additional ozone which enters the vessel through the perforations D The turpentine, water, and ozone thus become intimately mixed, with the result that hydrogen peroxide is formed and simultaneously absorbed by the water. The mixture of turpentine and water containing hydrogen peroxide in solution falls to the bottom of the chamber A, whence it can either he wit-hdrawn through the pipe H or conveyed through the pipe G back again to thevessel B for retreatment. The excess of ozone escapes from the chamber A by way of the exit-valve A and as it always carries with it uncondensed vapors of turpentine it is passed through suitable condensers in order to recover the turpentine.

It may sometimes be desirable to manufacture-hydrogen peroxide in s'izu for its direct application to articles which are required to be oxidized or bleached. Again, we have found under some conditions the substitution of steam for water gives in certain cases mo re satisfactory results. For the manufacture of hydrogen peroxide under these conditions we preferto employ the apparatus shown in Figs.

' holes in the plate D open into tapered passages made in nozzles D", which are screwed Z into that plate and which in turn'extend into tapered holes D in a cover D Between the plates D and D is a space D iinto which, by way of apipe G, steam is admitted for a purpose hereinafter explained, passing out in an upward direction around the nozzles D through the holes D The action is as follows: A turpentine or other suitable organic.

compound, either in a liquid or a vaporized form, is forced through the pipe F into the space D Ozone, which should be free from moisture or carbonic-acid gas, enters by the Steam enters the pipe E into the space D space D through the pipe G. The ozone passes from the space D through the spindles D nozzles D and holes D drawing up the turpentine from the space D through the annular passage-way D surrounding each nozzle D and out through the nozzles D and holes D in company with the ozone.

Steam from the space D passes up the annular passages surrounding the nozzles D the turpentine, ozone, and steam being delivered from the holes D in an atomized or vaporized condition into the vessel A. (Shown in Fig. 1.) If it is desired to manufacture the hydrogen peroxide in situ, then the turpentine, ozone, and steam may be delivered from the openings D directly onto the article to be bleached or otherwisetreated.

The chamber B, if desired, may be jacketed with steam or hot water, and the several jets of fluid need not be delivered concentrically with one another, but may be otherwise arranged in any desiredm anner so long as they mingle intimately at some common point of issue.

It is clear from the above description of the process that the oil of turpentine or any other suitable organic compound used in our process is not actually and entirely consumed in it, but plays only an intermediary role'in the reaction, so that if the whole process were carried out cautiously and quantitatively none or only a very small loss of the organic componndused would be experienced. In practice, however, we find that a small loss of the organic compound used occurs and also that in the case of several of the organic compounds here described a chemical change, known as polymerization, takes place. We. therefore prefer to dissolve or dilute the polymerized compounds in orwith the particular compounds originally used before using it over again in our process, and we have found that a higher yield of hydrogen peroxide is the result of such procedure. Thus the compound which we employ in our'process can, as is shown in the above, be used over again nearly indefinitely.

The whole process can, it dcsired,be made self-working or automatic and is carried out at the ordinary temperature. The concentration of the hydrogen peroxide produced depends upon'the length of timethe reaction is allowed to continue in our apparatuse. 9., after the reaction has gone on for only five to six hours solutions of three volumes of hydrogen peroxide are produced. Such or stronger solutions can, if a very high concentration of hydrogen peroxide is desired, be enriched in their contents of hydrogen peroxide by evaporation in vacuo.

As the hydrogen peroxide is soluble in water, it is therefore found to be entirely present in the water used in this process.

\Vhen-the process is considered to be fin ishedz. a, when the desired concentration is attained-the aqueous solution of hydrogen peroxide is'by any convenient means sepa rated from th e organic liquid employed, which as a rule is lighter and not miscible with the water. The aqueous solution of hydrogen peroxide so obtained usually still contains a trace of the organic compound employed or of any intermediary compounds which may have formed during the reaction, and as neither of these is soluble in water they will usually give to the aqueous solution of the hydrogen peroxide a turbid appearance. We have found, however, that if this turbid solution after having been separated is treated ,with ozone for quite a short time the traces of organic compounds contained therein will be decomposed or so altered in their composition that the solution is renderedperfectly clear.

The hydrogen peroxide produced by this process is more stable than when produced by any other process, and we have noticed that if it is exposed to the action of atmosphere it shows a tendency to absorb further quantities of oxygen. As the hydrogen peroxide obtained by our process is free from any bodies which may be injurious to the human organism, it can therefore be used in suitable concentrations, solutions, ormixtures, or with suitable additions, for internal and external therapeutical purposes; also, as a general antiseptic, disinfectant, deodorant, and preservative againstputrifaction, dzc. also, for the production of absolutely-pure oxygen for inhalations and for many other sanitary purposes.

It is well known that hydrogen peroxide on account of its being able to. give off one atom of active or available oxygen in a nascent form is a very strongoxidizing and bleaching agent; but its present high'cost has hitherto not allowed its wide application in these directions, As the hydrogen peroxide produced by our process is of a very low cost, it will become possible to apply it whenever a strong oxidizing or bleaching agent is resilks, yarns, feathers, ivory, bones, sugar syrups, oils, wood, cotton, and wool, for the re- IIO ,quiredas, for instance, for the bleaching of moval of stains, removal of the last traces of hypo in photography, of chlorine and sulfur dioxide in the old bleaching processes, and so on. For all these purposes the aqueous hydrogen peroxide produced by our process can be used directly according to methocls'which may be found most convenient and practicable for the particular purpose;

' but we have also devised a new process, by

means of which hydrogen peroxide, when required for several of the above-stated purposes, can be generated directly on the objects to be oxidized or bleached, and thereforeits action as being in situ be made much more effective and considerably less costly. This new process is carried out as follows: The object to be oxidized or bleachedfor example, cotton-is dipped into an emulsion of any of the already-mentioned organic compounds, preferably turpentine with Water, and is then exposed to the action of ozone in a suitable receptacle, vessel, or chamber. The hydrogen peroxide resulting from the reaction is thus produced directly on the fiber, and we have found that even articles which are very difficult to bleach by the best ordinary processes will be entirely bleached in a very short time by means of this process, or the same process can also be carried out'as follows: The articles to be bleached are dipped into the liquid organic compoundsay turpentine-and then placed in a chamber into which ozone and low-pressure steam are allowed to.enter. Hydrogen peroxide is formed on the fiber,and the article is bleached quickly and efficiently. v

The apparatus or chambers in which any of the above-stated bleaching or oxidizing processes are carried out are supplied with outlet-pipes leading into similar condensing apparatus, as previously described, the object of which is to condense the fumes of the organic compound or compounds used and thus obviate their loss.

Articles bleached by way of the above-described modifications of our process retain a faint odor of the organic compound which has been used for the production of hydrogen peroxide; but this odor is easily removed from the article by a short exposure to hot steam and ozone. In order not to waste hydrogen peroxide, we have found that all articles to be bleached should before bleaching be freed from fattymatters, dirt, &c., by any of the ordinary methods adapted for this purpose. lVe have found that the usually deleterious action upon the fiber experienced in most bleaching processes does not take place in our process. 6

The above-described production of hydrogen peroxide in situ, can be modified in numerous ways, according to the purpose for which it is required.

In an apparatus for producing hydrogen peroxide, the combination with the vessel containing the turpentine and ozone under pressure, a dish or receptacle D having a vertical annular flange, a second dish D carried by the first dish, leaving a space between said dishes, a cover for the dish D ,'a pipe leading from the space between the dish D and cover to the lower portion of the interior of the receptacle B,a pipe leading from the space between the dishes D and D to the top portion of the interior of the receptacle 1), tubular spindles D secured in the bottom of the dish D the nozzles carried by the plate D having tapered passages therein, into which the tubular spindles D open, a cover D having .tapered holes therein into which the nozzles extend, and a steam-pipe communicating with the space D between the cover D and plate D substantially as described.

In testimony whereof we have hereto set our hands in the presence of the subscribing witnesses.

SIGHUN D ROSENBLUM. CHARLES JOHN YARNOLD.

\Vitnesses to the signature of Sigmund Rosenblum:

WILMER M. HARRIS, 0. Ross. \Vitnesses to the signature of Charles John Yarnold:

MARIA YARNOLD, G. F. WARREN. 

